EP3328630A1

EP3328630A1 - Fluorinated polymer composition

Info

Publication number: EP3328630A1
Application number: EP16760125.1A
Authority: EP
Inventors: Anthony Bonnet; Cyrille Mathieu; Alejandra REYNA-VALENCIA; RAMFEL (Epouse WIEGERT), Barbara; Christophe DEGOULET
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2015-07-27
Filing date: 2016-07-27
Publication date: 2018-06-06
Also published as: WO2017017373A1; US10400097B2; AU2016299374B2; FR3039559B1; BR112017023900A2; AU2016299374A1; FR3039559A1; CN107787348A; CN107787348B; US20180134886A1; JP2018529783A

Abstract

The present invention concerns a fluorinated polymer composition, methods for producing same, and products that can be produced from said composition. More particularly, the invention concerns a thermoplastic polymer composition comprising the following components A, B and C: A - a polyvinylidene fluoride (PVDF) homopolymer comprising a fraction of ultra high molecular weight chains (UHMCF); B -a vinylidene fluoride (VDF) elastomeric copolymer and at least one other fluorinated comonomer copolymerisable with VDF, and C -a VDF homopolymer having a lower viscosity than component A.

Description

FLUORINATED POLYMERIC COMPOSITION

FIELD OF THE INVENTION

The present invention relates to a fluorinated polymeric composition, processes for the manufacture thereof, and products that can be made therefrom, including polymeric sheaths of flexible hoses used for transporting fluids from petroleum marine, or "off-shore", and land, or "on-shore") or gas.

TECHNICAL BACKGROUND

The transport of chemicals in the liquid or gaseous state in pipes has many advantages: it is more economical once the infrastructure is in place; it allows the transport of large volumes; it ensures a great security of supply, thanks to a regular flow; finally, it is safer than rail or road.

It is known to use, for the transport of liquid or gaseous products, metal or plastic tubes, or metal tubes coated with one or more polymeric layers. Depending on the fluid to be transported, these tubes must meet multiple requirements, particularly with regard to the properties of mechanical resistance (in particular to impact), elasticity, creep resistance, fatigue resistance, resistance to swelling, chemical resistance (to corrosion, oxidation, ozone, chlorinated products ...) and thermal resistance.

For example, pipes with one or more metal elements guaranteeing the mechanical rigidity but not sealed to transported fluids (for example steel or cast iron elements), as well as various layers based on polymeric compositions, are known for sealing transported fluids as well as thermal insulation. Typically, in the case of polymeric layers, the thickness / diameter ratio is of the order of 1/10. These polymeric compositions may be based on polyethylene, but this limits the temperature of use of the pipes to 60 ° C maximum. They may also be based on fluorinated polymers such as polyvinylidene fluoride also called polyvinylidene fluoride (PVDF), suitable for higher use temperatures, up to 130 ° C, and having good chemical resistance and good outfit thermal. However, PVDF is very rigid, and for this reason PVDF homopolymers are often formulated or used in admixture with vinylidene fluoride (VDF) copolymers and possibly plasticizer in order to reduce their rigidity.

Flexible hoses are also used for the transport of oil or natural gas extracted from submarine or terrestrial deposits. These pipes are formed of multilayer structures including polymeric sheaths and reinforcing layers of metal or composite materials.

Flexible hoses include, from the inside to the outside:

at least one internal sealing tube in contact with the transported fluid, consisting of a polymeric material,

one or more reinforcement layers surrounding said internal sealing tube, and

- an external protective sheath.

BE 832851 discloses fluorinated elastomers comprising a molar proportion of 50 to 85% of VDF and 15 to 25% of hexafluoropropylene (HFP), ie a mass proportion of 47 to 71% of VDF and 29 to 53% of HFP, which are used for the manufacture of PVDF molded bodies comprising from 1 to 30% by weight of fluoroelastomer. Such compositions, however, have limited extrudability, and do not allow the manufacture of tubes having a thickness / diameter ratio close to 1/10.

EP 1342752 discloses PVDF-based compositions comprising: (A) a PVDF homopolymer or a VDF-based copolymer; (B) a fluoroelastomer; (C) optionally a plasticizer. The fluorinated elastomer (B) is present in an amount of from 0.5 to 10 parts by weight per 100 parts of homopolymer or copolymer (A) and from 0 to 10 parts by weight of a plasticizer (C) with the condition further that the sum of (B) plus (C) is from 0.5 to 10.5 parts by weight. These compositions correspond to the following mass proportions: 89.5 to 90.5% of a PVDF homopolymer or a VDF-based copolymer (A); 0.5 to 9% of a fluoroelastomer (B); 0 to 9% of a plasticizer (C). The contents of fluorinated elastomer, less than 10%, do not allow to confer on the finished product characteristics of sufficient fatigue strength for the applications described above.

EP 608639 discloses polymeric compositions comprising, by weight, 60 to 80% of PVDF, 20 to 40% of a thermoplastic copolymer of VDF and another fluorinated comonomer (present in amounts of 5 to 25% in the copolymer), and from 5 to 20% of a plasticizer (relative to the sum of the PVDF and the copolymer). Among the thermoplastic copolymers envisaged include VDF / HFP copolymers. The HFP contents indicated in the copolymers which are disclosed in the examples are of the order However, these compositions undergo an extraction of the plasticizer in contact with certain chemical substances. As a result, the sheaths made with these compositions do not maintain a stable geometry, their volume and therefore their thickness tending to decrease over time.

This phenomenon can have a detrimental effect on the tightness of the tips located at both ends of the pipe. Indeed, the seal between the end of the pressure sheath and the body of the end-piece ("end-fitt") is done by a crimping process. that is to say clamping the sheath between two concentric parts bearing respectively on the inner and outer faces of said sheath.

An excessive decrease in the thickness of the sheath may therefore have the effect of degrading the crimping pressure and the sealing of the nozzle.

WO 2006/045753 discloses polymeric compositions comprising a PVDF homopolymer, a thermoplastic fluorinated copolymer and a third component which can be a plasticizer at up to 5% by weight, a perfluorinated polymer or a low molecular weight VDF polymer. The thermoplastic fluorinated copolymer may for example be a copolymer of VDF and another fluorinated comonomer, which may be present in a content of 5 to 25%. Typically, the mixture of PVDF homopolymer and fluorinated copolymer has an average intrinsic viscosity of less than 2 dl / g. Moreover, the polymeric composition has a melt apparent viscosity of less than or equal to 60,000 Pa.s at a rate gradient of 1 s- ¹ . However, the fluorinated polymeric compounds of the tubular structures made with such compositions In particular, when the structures are subjected to repeated movements due to marine currents, the fatigue strength of these fluorinated polymeric compounds is considered insufficient.

FR 2987624 discloses compositions comprising a PVDF homopolymer, an elastomeric fluorinated copolymer and a plasticizer. The copolymer has elastomeric properties which it confers on the fluorinated polymer compound and which makes it possible not only to increase the fatigue strength of said compound, but also to improve the cold strength. This is an essential difference with the object of the document WO 2006/045753, where, precisely, it is sought for compositions capable of forming non-elastomeric fluorinated polymeric compounds. However, the extraction of the plasticizer that occurs during the lifetime of the tubular structure, in addition to modifying the geometry of the sheaths (volume variation and thickness) as already mentioned above, gradually leads to a loss of properties initially provided. by plasticizing (flexibility, resilience), thus limiting the life of articles based on these compositions.

The object of the present invention is therefore to develop a novel polymeric composition based on a particular PVDF homopolymer, an elastomeric fluorinated copolymer and a third low viscosity fluorinated component, said composition having mechanical properties and improved chemical compared to known compositions, and which do not evolve over the life of the pipe in service to manufacture pipes and pipes remaining mechanically reliable in the long term especially for the monogaine pressure application used in the field off-shore.

SUMMARY OF THE INVENTION

The invention relates first of all to a thermoplastic polymeric composition comprising the following components A, B and C:

A- a vinylidene polyfluoride homopolymer (PVDF) comprising a fraction of very high molecular weight chains (FCTHM);

B- an elastomeric copolymer of vinylidene fluoride (VDF) and at least one other fluorinated comonomer copolymerizable with VDF, and

C- a homopolymer of VDFdéfmi by the ratio between the viscosity of the component A and its own viscosity, as indicated below.

Advantageously, the polymeric composition according to the invention is free of plasticizer.

Characteristically, component A is a PVDF homopolymer comprising a fraction of very high molecular weight chains (FCTHM), which are defined as chains with a molar mass greater than 3,000,000 g / mol, including non-transferred chains. or late transferred (FCNT) defined below. The other chains of component A are made by initiation and transfer or earlier transfer and have molar masses below 3,000,000 g / mol.

The mass proportion of chains of very high molar mass in component A is calculated by the following formula:

100 - (mass proportion of chains with a molecular weight of less than 3000000 g / mol expressed as polymethyl methacrylate equivalent).

The mass proportion of chains with a molecular weight of less than 3000000 g / mol expressed as polymethyl methacrylate equivalent in component A is determined by steric exclusion chromatography under the conditions described below. The dimethylsulfoxide (DMSO) to which sodium nitrate (NaN0 ₃ ) at a concentration of 0.1 mol / L has been added is both the eluent and the solvent of the samples. The concentration of the samples of component A prepared is of 2 g / L, the dissolution is made for 4 hours at a temperature of 95 ° C. The solution obtained is filtered using a syringe filter with a porosity of 0.45 μm and a volume of 200 μm is injected into the size exclusion chromatography line. This is typically provided with 2 columns in series of length 300 mm and diameter 8 mm, particle size 7μιη, porosity 100 Angstrom and 1000 Angstrom, regulated temperature at 50 ° C. Polymer Standards Service columns referenced PSS PFG 1000 Angstrom and PSS PFG 100 Angstrom were used. The detection at the column outlet is done by a differential refractometer. It is also regulated in temperature at 50 ° C. The standards used for calibration of the columns are narrow polymethyl methacrylates (PMMA) covering the column separation range.

The proportion of chains of very high molecular weight (especially chains not transferred or transferred late) thus calculated represents up to 50% by weight of component A, including the terminal.

Component A has a melt flow index of less than or equal to 15 g / 10 min, advantageously less than or equal to 10 g / 10 min, preferably less than or equal to 5 g / 10 min, according to the standard ISO 1,133.

Component B is present in the composition at a mass content higher than

10%. According to one embodiment, the fluorinated comonomer copolymerizable with VDF is chosen from vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene (CTFE), 1,2-difluoroethylene, tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro (alkyl vinyl) ethers such as perfluoro (methylvinyl) ether (PMVE), perfluoro (ethylvinyl) ether (PEVE), perfluoro (propylvinyl) ether (PPVE), perfluoro (1,3-dioxozole); perfluoro (2,2diméthyl-l, 3dioxozole) (PDD), the product of formula CF2 = CF0CF2CF (CF3) OCF2CF2X wherein X is S0 ₂ F, C0 ₂ H, CH ₂ OH; CH ₂ OCN or CH ₂ OPO ₃ H, the product of formula CF 2 = CFOCF 2 CF 2 SO 2 F; the product of formula F (CF 2) nCH 2 OCOF = CF 2 in which n is 1,2,3,4 or 5, the product of formula R 1 CH 2 OCOF = CF 2 in which R 1 is hydrogen or F (CF 2) z and z is 1, 2, 3, or 4; the product of formula R30CF = CH2 in which R3 is F (CF2) z and z is 1, 2, 3, or 4 or alternatively perfluorobutylethylene (PFBE), fluoroethylenepropylene (FEP), 3,3,3-trifluoropropene, 2-trifluoromethyl-3,3,3-trifluoro-1-propene, 2,3,3,3-tetrafluoropropene or HFO-1234yf, E1,3,3-tetrafluoropropene or HFO-1234zeE, Z- 1,3,3,3-tetrafluoropropene or HFO-1234zeZ, 1,1,2,3-tetrafluoropropene or HFO-1234yc, lel, 2,3,3-tetrafluoropropene or HFO-1234ye, 1,1,3, 3-Tetrafluoropropene or HFO-1234zc and chlorotetrafluoropropene or HCFO-1224.

According to a preferred embodiment, the comonomer is hexafluoropropylene

(HFP).

According to one embodiment, the elastomeric copolymer is present in the composition in a mass proportion of more than 10 to 40%, advantageously 15 to 40%, preferably 17 to 35%, inclusive.

The proportion by weight of comonomer in the copolymer is greater than 25%. Advantageously, it is: greater than or equal to 26%, and / or less than or equal to 40%, preferably less than or equal to 37%.

Component C is a VDF homopolymer having a lower viscosity than component A; it is present in the composition in a mass proportion ranging from 1 to 20%, in particular from 2 to 18% and preferably from 5 to 15%.

The ratio of the apparent melt viscosities of components A and C is greater than or equal to 5, in particular greater than or equal to 10 and preferably greater than or equal to 50. This ratio is less than 500, preferably less than 400 The apparent melt viscosities of components A and C are expressed in Pa.s and measured on a capillary rheometer at a temperature of 230 ° C. and a shear of 100s ^-1 .

According to one embodiment, the thermoplastic polymer composition consists of:

A - a polyvinylidene fluoride homopolymer comprising a fraction of chains of very high molar mass (FCTHM);

B - a VDF-HFP copolymer, and

C - a homopolymer of VDF,

components A, B and C being as defined herein.

The subject of the invention is also a process for the manufacture of the above composition, comprising the mixture of homopolymer, copolymer, fluorinated modifier and any additives. This manufacturing method comprises any method which makes it possible to obtain a homogeneous mixture of the various constituents. Among these methods, mention may be made of the mixture in the molten or dry state.

More particularly, the composition according to the invention is prepared by melt blending all the constituents, on a compounding tool such as a twin-screw extruder, a co-kneader or an internal or cylinder mixer. According to one embodiment, the homopolymer of PVDF (component A) and the elastomeric copolymer (component B) are in dry form during mixing, preferably in the form of powders, and preferably the mixture with component C is carried out at room temperature. the molten state on a compounding tool such as a twin-screw extruder, a co-kneader or an internal or cylinder mixer.

According to one embodiment, the above process comprises mixing the PVDF homopolymer (component A) and the elastomeric copolymer (component B) in latex form, drying the homopolymer and copolymer mixture, and the Combination of the dried mixture with the component C is carried out in the molten state on a compounding tool such as a twin-screw extruder, a comalizer or an internal or cylinder mixer.

The composition according to the invention obtained by the manufacturing method described above can then be transformed for use in the form of pipes or cables, in particular using tools such as an extruder equipped with a suitable die. .

The subject of the invention is also, in general, a tube comprising at least one layer consisting of the composition according to the invention.

According to one embodiment, said tube is intended to be used as a polymeric sheath of flexible hoses used for transporting fluids from oil and gas operations. In this form, the sheath can be used, in combination with at least one reinforcing layer and possibly an outer protective sheath, as a flexible hose for transporting fluids from oil or gas operations.

According to one embodiment, said tube is a land transport pipe of products in the gaseous state.

According to one embodiment, the aforementioned pipe is for the transport of gaseous products, especially for the transport of hydrogen, oxygen, water vapor, carbon monoxide, ammonia, hydrogen fluoride, hydrochloric acid, hydrogen sulphide, any gas from the cracking of hydrocarbons, or mixtures thereof.

According to one embodiment, said tube is intended for the ground transportation of products in the liquid state, for example the transport of water, solvents, petroleum products, or mixtures thereof.

According to one embodiment, the aforementioned pipe is a service station underground pipe or a vehicle fuel supply pipe. The invention also relates to an electric cable made from the above-mentioned composition.

The invention also relates to the use of the composition described above, for the manufacture of pipes or electrical cables.

The present invention overcomes the disadvantages of the state of the art.

It provides more particularly a new polymeric composition having improved mechanical and chemical properties that do not evolve during the life of the material while being easily transformable by extrusion or co-extrusion in the molten state.

This composition makes it possible to manufacture pipes and pipes that remain mechanically reliable in the long term. The composition according to the invention is particularly suitable for the manufacture of polymeric sheaths for flexible hoses for the transport of fluids from petroleum operations and pipes for the transport of liquid or gaseous synthesis products (for example for the transport of hydrogen). . As already mentioned, the composition according to the invention is particularly suitable for being implemented by extrusion or coextrusion, which allows its transformation into tubes.

This is accomplished by combining PVDF elastomeric copolymer with non-transferred chain fraction PVDF homopolymer, the copolymer being present in the final composition in a proportion of greater than 10%; and adding a PVDF homopolymer of low viscosity in the composition at a mass content of at most 20%. The use of a PVDF homopolymer with a very high molecular weight gives the composition improved cold impact and fatigue properties. The association with a copolymer of elastomeric nature also allows the formation of a biphasic system in which the elastomer nodules act as a reinforcement, which leads to cold shock properties and fatigue still improved. Finally, the addition of a PVDF homopolymer of low viscosity makes it possible to lower the viscosity of the composition in order to make it easily transformable by extrusion or coextrusion in the molten state. In addition, the use for this purpose of a PVDF homopolymer of lower viscosity than that of component A (component C) makes it possible to obtain a 100% fluorinated composition, in which all the components are compatible and which do not encounter any problems. selective degradation and / or extraction of the plasticizer in contact with certain chemical substances, known during the use of a plasticizer such as dibutyl sebacate (DBS). The use of a PVDF homopolymer of low viscosity in place of an extractable plasticizer makes it possible to preserve the mechanical properties of the composition over time, in particular the resistance to impact and fatigue and to avoid the volume variation of the objects obtained from the composition. In particular when the composition is used for the manufacture of polymer sheaths for flexible hoses intended for the transport of fluids from petroleum operations and pipes for the transport of liquid or gaseous synthesis products (for example for the transport of hydrogen), the hose considered is mechanically reliable in the long term and its volume is conserved over time which allows a simplified design of the tips.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The invention is now described in more detail and without limitation in the description which follows.

According to a first subject, the invention relates to a thermoplastic polymer composition comprising the following 3 components:

A - a PVDF homopolymer comprising a fraction of chains of very high molar mass (FCTHM);

B - an elastomeric copolymer of VDF and at least one other fluorinated comonomer copolymerizable with VDF, and

C - a PVDF homopolymer of low viscosity.

Component A is a PVDF homopolymer comprising up to 50% by weight of chains of molar mass greater than 3,000,000 g / mol, representing the fraction of chains of very high molar mass. Said fraction is advantageously between 20 to 50%, preferably 25 to 45% by weight of component A.

These polymers are known, their preparation has been described by the Applicant in the document EP 1279685.

These polymers are prepared by a synthesis process, especially in emulsion, in which:

a dispersion of VDF (vinylidene fluoride) in water is produced, optionally with the aid of a surfactant, the said dispersion being initially brought into contact with a non-organic initiator soaked in water capable of causing the polymerization of the monomers; and then, a portion of the PVDF having been formed in the presence of the non-organic initiator dissolved in water, is added: either (i) a chain transfer agent capable of propagating the polymerization, said polymerization is then initiated by a non-organic initiator soluble in water or by an organic initiator, or (ii) an organic initiator capable of to also carry out chain transfer and optionally a non-organic initiator soluble in water.

The principle of this process is based on the formation, at the beginning of polymerization, of a fraction of very high molecular weight macro-molecular chains, produced before the introduction of transfer agent (or before a transfer-type secondary reaction or termination helping to strongly limit the chain length) and without initiator capable of inducing a transfer reaction. The reaction therefore starts without a transfer agent (CTA), and the first charge of CTA is injected at a conversion rate of the monomers, for example of the order of 5% by weight. The necessary dose of CTA can then be introduced incrementally or continuously, the total amount and the rate of introduction to adjust the average molar mass of the polymer. In the case of a single injection of transfer agent, the product obtained will show a specific molecular weight distribution with a first population of very high mass and a second population of limited mass. The polymerization step after addition of the first dose of transfer agent can also be carried out under the effect of an organic initiator whose contribution to the transfer reactions will be more or less important.

In the particular case of an organic initiator having a transfer effect sufficient to adjust the molecular weight, it is also possible to dispense with the transfer agent itself without changing the nature of the invention. In this case, the FCTHM is still obtained during the first polymerization step in the presence of the non-organic initiator, and a second fraction of moderate molar mass is formed under the sole action of the organic initiator.

The rate of conversion of the VDF before the first injection of CTA determines the fraction of very high-mass chains (in particular chains not transferred or transferred late) formed without transfer agent called "non-transferred chain fraction". Then the very high mass chains having been formed the number of injections or the rate of introduction of the CTA determines the distribution of the molar masses of the PVDF fraction which is not very high mass. The total volume of CTA is not a critical parameter. It must be adjusted to set the average molar mass of the polymer that is associated with the melt viscosity. The volume of water in which the dispersion of the monomers is carried out, the amounts of surfactant, initiator and CTA are readily determinable by those skilled in the art. The polymerization is carried out in a stirred reactor, then the PVDF is separated everywhere (it is in the form of solid particles) and the water is separated. These techniques are known per se and are described in US Patents 4025709, US 4569978, US 4360652, EP 626396 and EP 0655468. Advantageously, the aqueous emulsion is polymerized at a temperature of 50 to 130 ° C. Preferably, the polymerization is carried out at an absolute pressure of 40 to 120 bar.

With regard to the surfactant is thus meant any product capable of dispersing the monomers in water to facilitate their polymerization. US Pat. No. 4,025,709, US Pat. No. 4,560,478, US Pat. No. 4,360,462, EP No. 6,046,666, EP No. 2,059,463 and EP No. 2,089,463 describe the methods for synthesizing PVDF by aqueous emulsification of VDF and its polymerization, there are numerous surfactant formulations. The amount of surfactant introduced at the start or during polymerization may be between 0.01 and 5 parts per 100 parts of water present in the initial charge of the reactor.

As regards the water-soluble non-organic initiator capable of causing the polymerization of VDF, inorganic peroxides, for example in the form of salts, such as potassium or sodium persulfate, may be mentioned. The amount of initiator may range from 0.002 to 0.2 parts per 100 parts of monomers consumed in the reaction. Various coreactants well known to those skilled in the art may also be added to these inorganic peroxides to increase their rate of decomposition or to lower their temperature of use.

With regard to the organic initiator optionally used to continue the reaction, there may be mentioned essentially hydrocarbon peroxides, such as di-tert-butylperoxide, di-cumylperoxide or benzoyl peroxide, dialkyl percarbonates, such as diethyl or di-so-propylpercarbonate, peracids or peresters, such as t-butyl perpivalate; t-amyl perpivalate or t-butyl peroxybenzoate.

With regard to the transfer agent, is meant any product that limits the molecular weight of the polymer while propagating the polymerization reaction. By way of example, mention may be made of acetone, isopropanol, methyl acetate, ethyl acetate, diethyl ether, n-butyl acetate, diethyl malonate and diethyl carbonate and different chlorofluorocarbon compounds. The amount of transfer agent depends essentially on its nature and the average molar mass desired for the polymer fraction obtained in its presence, which conditions the average viscosity of the final product. Preferably, the transfer agent used represents from 0.01 to 5 parts per 100 parts of monomers consumed in the reaction.

As regards the proportion of very high molar mass chains (particularly non-transferred or late-transferred chains), it can represent up to 50% the weight of the component A and it is advantageously between 20 to 50%, preferably from 25 to 45% inclusive.

In one embodiment, the PVDF homopolymer used in the context of the invention as component A has a melt flow index of less than or equal to 15 g / 10 min, advantageously less than or equal to 10 g / 10 min, and ideally less than or equal to 5 g / 10 min, according to ISO 1133 (230 ° C, 12.5 kg), in order to guarantee good mechanical strength properties.

Component B is present in the composition at a mass content greater than 10%). According to one embodiment, the elastomeric copolymer is present in the composition in a mass proportion of more than 10 to 40%, advantageously 20 to 40%, preferably 25 to 35%, inclusive.

According to some embodiments, the mass content of copolymer in the composition is greater than or equal to 11%, or 12%, or 13%, or 14%, or 15%, or 16%>, or 17%>, or 18%, or 19%, or 20%, or 21%, or 22%, or 23%, or 24%, or 25%, or 26%, or 27%, or 28%, or 29%, or 30%, or 31%, or 32%>, or 33%>, or 34%, or 35%, or 36% , or 37%, or 38%, or 39%.

According to some embodiments, the mass content of copolymer in the composition is less than or equal to 39%, or 38%, or 37%, or 36%, or 35%, or 34%, or 33%. %, or 32%, or 31%, or 30%, or 29%, or 28%, or 27%, or 26%, or 25%, or 24%, or 23%. %, or 22%, or 21%, or 20%, or 19%, or 18%, or 17%, or 16%, or 15%, or 14%, or 13%. %, or 12%, or 11%.

According to one embodiment, when the comonomer is HFP, the mass proportion of HFP in the copolymer is greater than 25%. Advantageously, it is: greater than or equal to 26%, and / or less than or equal to 40%, preferably less than or equal to 37%.

The mass proportion of HFP in the elastomeric copolymer is preferably estimated by nuclear magnetic resonance (NMR). In particular, the ¹⁹ F NMR method described below can be used. The copolymer samples are dissolved in a 5 mm diameter NMR tube. The copolymer samples are dissolved in tetrahydrofuran-d8 (THF-d8) at 60 ° C. An amount of copolymer (about 10 mg) is placed in a tube and solvent is added to fill 5.5 cm of tube (about 0.75 mL solvent). A heating block is used to bring the samples to the desired temperature. The samples are heated for at least one hour until dissolution of the solid and disappearance of the gel. The tubes are returned to check for frost.

Typically the spectra are acquired on a Bruker Advance type spectrometer operated at 60 ° C. and are analyzed according to a method analogous to that described in "Composition and Sequence Distribution of Vinylidene Fluoride Copolymer and Terpolymer Fluoroelastomers". Determination by NMR spectroscopy and ¹⁹ F correlation With Some properties ". M. Pianca et al, Polymer, 1987, vol.28, 224-230. However, the integration of the group CF instead of the group CF3 is used.

Preferably, the elastomeric copolymer used for the preparation of the composition according to the invention is devoid of homopolymer.

The copolymer can be manufactured by the method described in the publication by M. Pianca et al supra.

By "elastomeric" copolymer is meant, as defined by ASTM in Special Technical Publication No. 184, a material capable of being stretched at room temperature up to twice its own length and which once released after holding on for 5 minutes, resumes to within 10%, its initial length at the same time.

The fluoroelastomers that may be used in the context of the invention may be chosen from true elastomers or polymeric resins serving as the basic constituent for obtaining true elastomers.

Component C is a low molecular weight VDF homopolymer; it is present in the composition in a mass proportion ranging from 1 to 20%, in particular from 2 to 18% and preferably from 5 to 15%.

Advantageously, the ratio of the apparent melt viscosities of the components A and C is greater than or equal to 5, in particular greater than or equal to 10 and preferably greater than or equal to 50. This ratio is less than 500, preferably less than 500. at 400. The apparent melt viscosities of components A and C are expressed in Pa.s and measured on a capillary rheometer at a temperature of 230 ° C. and a shear of 100s ¹ .

In addition to component A, copolymer B and component C, the composition according to the invention may comprise at least one additive and / or at least one filler and / or electrically conductive particles and / or inorganic or organic pigments or dyes. Among the possible fillers, non-limiting mention may be made of mica, alumina, talc, carbon black, graphenes, expended graphites, carbon nanotubes, glass fibers and calcium carbonate.

Among the possible additives, UV stabilizers (preferably with the exception of agents of the IRGANOX ^® type), flame retardants, heat stabilizers, manufacturing auxiliaries (preferably with the exception of polyolefins and in particular ethylene-based polymers).

When present, the above compounds, distinct from the FCTHM PVDF, the copolymer and the PVDF homopolymer of low mass, are present at a level of at most 20%, preferably at most 15%, or at 10%. not more than 7% or not more than 5% or not more than 3% or not more than 2% or not more than 1% (in mass proportion to total composition).

The subject of the invention is also a process for the manufacture of the above composition, comprising mixing the PVDF homopolymer (component A), the elastomeric copolymer (B) and the low molecular weight PVDF homopolymer (component C). . This manufacturing method comprises any method which makes it possible to obtain a homogeneous mixture of the various constituents. Among these methods, mention may especially be made of the mixture in the molten or dry state. More particularly, the composition according to the invention is prepared by melt blending of all the constituents, on a compounding tool such as a twin-screw extruder, a comalizer or an internal or roll mixer.

According to one embodiment, the FCTHM PVDF homopolymer (component A) and the copolymer (component B) are in dry form during mixing, preferably in the form of powders.

According to one embodiment, the above method comprises premixing components A and B in latex form (or emulsions), and then drying the premix in a powder. An alternative is to pre-mix the component A in latex form with the copolymer B in powder form (or vice versa), then to dry this type of premix into a powder.

The component C in the form of powder or latex, as well as any additives may be incorporated into the compositions during the mixing of the PVDF and the copolymer, or else mixed with one or the other of these constituents prior to their mixing, or else during the premixing of the PVDF and the copolymer according to the pre-mixing techniques described above.

The composition according to the invention makes it possible to manufacture: - all types of pipes for the transport of gaseous or liquid products, in particular intended to transport gaseous products for the synthesis of chemicals or intended to transport individual consumer products, whether industrial or public,

- umbilicals and flexible tubes used on-shore and off-shore to contain and / or transport crude oil, natural gas, water and other gases used for drilling, as defined in API 17J standards , API 17K, API 16C and API 15S.

Claims

A thermoplastic polymeric composition comprising the following components A, B and C:

A - a vinylidene polyfluoride homopolymer (PVDF) comprising up to

50% by weight of a fraction of very high molecular weight chains (FCTHM) which are chains having a molar mass greater than 3,000,000 g / mol, component A having a melt flow index of less than or equal to 15,000 g / 10 min, according to ISO 1133;

B - an elastomeric copolymer of vinylidene fluoride (VDF) and at least one other fluorinated comonomer copolymerizable with VDF, and

C - a homopolymer of VDF, as

the ratio of the apparent melt viscosities of components A and C, expressed in Pa.s, being greater than or equal to 5 and less than 500, the apparent melt viscosities of components A and C being measured on a Capillary rheometer at a temperature of 230 ° C and a shear of 100s ^-1 .

2. The composition according to claim 1, wherein said FCTHM homopolymer PVDF comprises a fraction of chains of very high molar mass, representing between 20 to 50%, preferably 25 to 45% by weight of the component A.

3. Composition according to one of claims 1 and 2 wherein the mass proportion of very high molecular weight chains in component A is calculated by the following formula:

100 - (mass proportion of chains with a molecular mass of less than 3000000 g / mol expressed as polymethyl methacrylate equivalent),

said mass proportion of chains of molecular weight lower than 3000000 g / mol expressed in polymethyl methacrylate equivalent being determined by steric exclusion chromatography.

4. Composition according to one of claims 1 to 3 wherein component A has a melt flow index of less than or equal to 10 g / 10 min, preferably less than or equal to 5 g / 10 min, according to the ISO standard. 1,133.

5. Composition according to one of the preceding claims wherein the elastomeric copolymer is present in a mass proportion of more than 10 to 40%, preferably 15 to 40%, preferably 17 to 35%.

6. Composition according to one of the preceding claims wherein the mass proportion of comonomer in the elastomeric copolymer is greater than 25%, preferably greater than or equal to 26%, and / or less than or equal to 40%, preferably less than or equal to at 37%.

7. Composition according to one of the preceding claims wherein said comonomer is hexafluoropropylene (HFP).

8. Composition according to one of the preceding claims wherein the mass proportion of component C is 1 to 20%, in particular 2 to 18% and preferably 5 to 15%.

9. Composition according to one of the preceding claims wherein the ratio of the apparent viscosities in the molten state of components A and C, expressed in Pa.s, is greater than or equal to 10 and preferably greater than or equal to 50, and it is less than 500, preferably less than 400, the apparent melt viscosities of components A and C being measured on a capillary rheometer at a temperature of 230 ° C and a shear of 100s ¹ .

10. Composition according to one of claims 1 to 9, said composition consisting of components A, B and C.

The composition of claim 10 wherein component B is a VDF-HFP copolymer.

12. Composition according to one of claims 1 to 9, said composition comprising at least one additive and / or at least one filler and / or electrically conductive particles and / or inorganic or organic pigments or dyes.

13. A method of manufacturing a composition according to one of claims 1 to 12, comprising the mixture of components A, B, C and any additives.

The process according to claim 13, wherein components A and B are in dry form, preferably in the form of powders, when mixing with component C, and mixing is carried out in the molten state.

15. The method according to claim 13, comprising mixing the components A and B in latex form, drying said latex, and melt-blending the dried mixture with the component C.

16. Pipe comprising at least one layer consisting of a composition according to one of claims 1 to 12.

17. Polymeric sheath of flexible hoses used for transporting fluids from oil and gas operations, said sheath consisting of a composition according to one of claims 1 to 12.

18. Use of the pipe according to claim 16, for the transport of synthesis products in the gaseous state, in particular for the transport of hydrogen, oxygen, water vapor, carbon monoxide, ammonia, hydrogen fluoride, hydrochloric acid, hydrogen sulfide, any gas from the cracking of hydrocarbons, or mixtures thereof.

19. Use of the pipe according to claim 16 for the transport of products in the liquid state, in particular for the transport of water, solvents, petroleum products or mixtures thereof.

20. Use of the pipe according to claim 16 as underground pipe for service station.

21. Use of the pipe according to claim 16 as a fuel supply pipe for vehicles.

22. Electrical cable made from the composition according to one of the claims

23. A hose used for transporting fluids from oil and gas operations, comprising a polymeric sheath consisting of a composition according to one of claims 1 to 12, said sheath being in contact with the transported fluid, at least one reinforcing layer. and an outer protective sheath.